Preparation of stable binary motor fuel



March 6, 1945. v A` 5. WOLFNER l l l 2,371,010

PREPARATION 0F STABLE BINARY MOTOR F-UEL Filed July 29, 194].V

. FEI-"L UA* constituents.

Patented Mar. 6, 1945 y Mannion 2.311.010 or annui anular Moron. FUEL Alfred S. Wallner, Long Beach-QN. Y.

Application July 29, 1941, Serial N0. 404,599 In Mexico April 2,8, 1941 The invention described herein relates to thel production of a motor fuel composed of gasoline and ethyl alcohol and represents a-simplemethod of preparation which improves considerably the, working methods known up to now.

Blends of alcohol and motor gasoline have been the object of numerous economic and technical studies, and such blends have been made in various countries. The methods of blending which have been principally used heretofore are three:

1. Blending of.motor gasoline with concen. trated ethyl alcohol of maximum 95.4% strength containing at least 4.6% water.

2. Preparationof a ternary mixture bybIending motor gasoline with concentrated alcohol of maximum 95.4% strength and with industrial benzol. y

3. Blending of absolute alcohol with motor gasoline.

The blendedmotor fuel composed only of gaso# line andconcentrated alcohol'does Anot give en` A tire satisfaction because the miscibility of the two components is not complete. The miscibility is a function of the temperature, of the' water con,- tent of the concentrated alcohol. and of the proportion in which the two components are blended. As a matter of fact, `separation of the blend will take place when the temperature is lowered; and

(Cl. 21m-42),'

best known arethe following:

two layers of different gravity will form, an upper g layer composed of gasoline containing a small percentage of alcohol which is practically anhydrous and a lower layer composed |of the larger .part of the alcohol originally incorporated'into the motor fuel together with nearly all the water which the alcohol initially contained and a portion of the gasoline composed of its most volatile It is evident that the separation into two layers at low temperatures presents a serious inconvenience for the good operation of a motor car and that such a formula for blending alcohol and gasoline is not desirable.

When commercial benzol or any other similar material is added in considerable proportionto the blend of gasoline and 95% alcohol,`a.motor fuel is obtained that' has a good stability. How ever, such a blend may be otherwise objectionable inasmuch as the benzolor other material to be added may not be generally available in sumcient quantity o1' at a price which vwould allow its use without a noticeable increase in the cost of the resulting motor fuel. Thel quantity -of'benzol to be added in order to obtain good stability at low temperatures ofthe blended motor fuel varies according to the climatic conditions and the concentration of the alcohol, but very often the quantity of benzol to be added is of the order of the quantity of concentrated alcohol incorporated into the motor fuel.

` Absolute ethyl alcohol ls a very strong organic solvent and is completely miscible with gasoline at any temperature and in any proportion. Commercial blends of motor gasoline and absolute alcohol form a motor fuel-of perfect stability that has considerablevalue for the motorist because of the fact that alcohol, incorporated into gasoline in moderate proportions, will increase the anti-knock value'of the gasoline and give other desirable characteristics thereto. The prepara. n tion of completely dehydrated alcohol to be added to .motor gasoline has been solved technically, and

tion.'

The purpose of the present invention is to avoid the difficulties of the known methods of preparing absolute alcohol which is to be blended with motor gasoline and to provide aiprocess that permits the direct preparation of a stable motor fuel from the two components with a'saving inproduction cost and the plant equipment'required.

Normally, for the production ofabsolute alcohol, chemical or physical methods are used. The

In the chemical dehydration of alcohol, burnt lime or alkaline salts, the latter often suspended in glycerine, are used to remove the water. These methods, however, have not found important industrial application on accountA of the difficulties of regeneration of the dehydrating chemical and on account ofthe losses of alcohol incurred.

The physical process oi' dehydrating alcohol is based on-azeotrop'ic distillation. In an ideal blend of two liquids, the partial vapor pressure of each component is directlyproportional to the molal concentration of each, and the total vapor pressure is equal to the sum of the partiaivapor pressures. According to the laws of the ideal gases, the composition of the vaporsformed during disi vtillation is proportional to the partial vapor rpresof its components; and their sum, the total vapor Lpressurel does not follow a straight line between v the .vapor pressures of the two pure products but has an intermediate maximum or minimum point.

Such a maximum or minimum total vapor pressure corresponds to the distillation of an azeotropic mixture'and representsv the limit -of concentration that can be obtained by fractional distillation.

-For this reason, the recticationof aqueous 5 .alcohol at atmospheric pressure cannot give a product containing more than 95.4% by weight of alcohol. 'A third material must-be added'to the water-,alcohol 'system' in order to break the azeotrope. Under these conditions, a new form of vaporization equilibrium is obtained until one industrial installations now exist' for its produc# or the tin-ee constituents is eliminated. In the case of the distillation of absolute alcohol, the

-vapors liberated contain a greater proportion of.

water than the liquid; and'the dehydration of the alcohol .is thereby accomplished. AIt is then,

necessary to recover from theY condensed vapors the material which has been used for the removal of thel water. Thismaterial is also to be recovered from the distillation residue which other-v wise would be abinary blend of dehydrated alcohol and the third material used for the removal of the water. A third lmaterial which may be utilized for the removal of the water comprises benzol, ether, trlchlorethylene, and the like. y

The known processvof manufacturing absolute ethyl alcohol comprises the'following phases:

(A) The concentration and rectiiication of aqueous alcohol to yield a. concentrated alcohol absolute alcohol must not be contaminated with the third material for many reasons.

The principal features of the present invention are to utilize as a third material for the removal of water from concentrated alcohol to be used for the preparation of a stable binary motor fuel the gasoline which'will be a constituent of the stable motor fuel and to arrange the dehydratlng equipment in such a manner that there is obtained directly as a nnal product the stable Abinary motor fuel desired. It is evident that this new method presents a simplification of the work required inasmuch as the separation of the thirdmaterial used for the removal of the water is no longer necessary after the dehydration of the alcohol. The heat required for ,operating by this new method as compared with the known of 95.4% strength as an overhead product and a residue consisting of water, from which practically all the alcohol has been removed.

(B) The azeotropic fractional. distillation o the concentrated alcohol. to which a third ma.- terial has been added for .the removal of the water. Absolute alcohol is obtained as a residue,

from which the whole of the third materialv used for the removal of the waterV has been separated. The overhead product is composed of all the benzol ol" other third material, of alcohol, and of all the water which was originally contained in the concentrated alcohol. The overhead product er separation into two layers. The upper layer, containing very little water, .is returned to the main column as reflux whereas the lower layer is introducedinto another fractionating tower wherein there is effected. l

methods of producing absolute alcohol is naturally much reduced, and the conduct of the op erations is simplified.

/ The equipment for the dehydration of a blend of concentrated alcohol and gasoline in accordance with my inventionmay be set up for continuous operation or for discontinuous or batch op eration. In principal, the apparatusconsists of s a fractionating column having the necessary is subcooled after condensation to effect a sharpnumber of fractionatlng trays. lInto the uppersection of this column are introduced all ofthe concentrated alcohol to be dehydrated and all or part of the gasoline which is to be incorporated into the binary motor fuel. is also equipped for receiving reflux.

From this column there are withdrawn as a residual product a stabilized binary motor fuel a5 free of water and as an overhead product the v(C) A fractional distillation of the lower layer v for the purpose o f separating the third material from diluted alcohol, which is withdrawn as a residue. The overhead comprising the third niaterial ilows back to the main column for .dehydrating purposes, and the residue passes into a third distillation tower wherein there is accom` plished.' A l `(D) A rectiilcation for concentratingfthe alcohol, which is obtained .as an overhead product and which is added tol the main charge of concentrated alcohol to be dehydrated. Alcohol'- free water is withdrawn as a residue.

The process of dehydrating concentrated alcohol by azeotropic distillation canftherefore. be considered as consisting of two main distille..

tion phases and one concentration step as follows:

ternary azeotropic vapors. These vapors are' subjected to complete condensation and to a separation into two distinct layers preferably under the .innuence of forced cooling or of a com- 40 plementary action such, for example, as the addition of water to the heavy layer simultaneously or consecutively to the subcooling. .'The sepaheavier layer is subjected to complementary treatration of the overhead condensate into'two. layeds produces, a lighter, upper layer composed only of light gasoline and nearly completely dehydrated alcohol and a heavier, lower layer composed of substantially all the water, of alcohol,

and ofl a little gasoline.

' The lighter'layer is separated and is returned to the main fractionating column as reflux. The

ment to separate the waterfrom the other materialsv which are returned to the main column.

1. Azeotropio distillation loi! n ternary blend or ethyl alcohol, water, and a third material useddehydration of the for the removal of water (for alcohol).

2. Distillation of a binary blend composed of ethyl alcohol and the third material used for the removal'of the water for the elimination of the third material (to Obtain absolute alcohol).

inasmuch as 4this operation causes certain losses which must be made up by the addition of more of the third material; on the other hand,lthe

A classical method for treatment of the heavierv layer is-to fractionally distill it in two stages. In the iirst stage, gasoline is removed in vapor form;

in the second stage, the residue of the first stage is separated into concentrated alcohol as an overhead product4 and water as a residue. The alcohol and gasoline so recovered are returned to the main column in either vapor or vliquid form. It should be noted that the overhead gasoline vapors from the first stage may contain some alcohol.'

Y column il fitted with the usual fractionating trays' This apparatus may also be used for the preparation of a stable binary inotoil fuel containing alcohol if the material to be incorporated is other thanethylalcohol. )A The diasrammatical flow sheet attached hereto gives details of a typical apparatus for continuous operation in accordance with the present invention.

The apparatus includes a main distillation (not shown) or other means to assure an intimate contact between the ascending'V vapors and the The column l descending liquid. A source of heat such as a steam reboiler coll I2 is positioned in a lower part of the column, and the desired product comprising the stable binary alcohol-gasoline motor fuel blend is drawn olf through line I4 as by pump IB. Such blend of gasoline and anhydrous alcohol generally'contains in the range of v10 to 25% alcohol. The outlet temperature cf this product must be at least equal to 1 the boiling point of the binary system of gasoline and alcohol in order to assure that all the water has been eliminated in vapor form towards the upperpart of the column inas-l much as the ternary azeotrope of water, gasoline, and alcohol has a lower boiling point. To assure that the motor fuel blend is sumciently subjected 'toreboilin'g heat, lI may provide a weir or partition It to retain the liquid in contact with reboiling coil |2 for the desired length of time. Liquid level control I3 may be provided to control the withdrawal of the blended motor fuel through line I4. For control of the reboiling temperature, a controlvalve I8 for the'admission of the heating steam is provided. The blended product is passed in heat exchange with the gasoline introduced through line in a heat exchanger 2| and iiows -of gasoline, alcohol, and water from contact of the ascending vapors coming from the lower and middle parts of the column with the descending liquid composed of concentrated alcohol to be dehydrated introduced through linel and of the redux liquids introduced through line 26. Alcohol admission control valves 21. and reflux admission control valves 23 may be provided. The azeotropic vapors formed of water, light gasoline. and alcohol ilow through line to condenser 32 wherein they are completely condensed. The resulting condensate is subcooled in.. cooler 34 in order to facilitate its separation into layers. The temperature at the top of the tower maybe determined by a suitable pyrometer 35.

The overhead condensate enters separator 36. which is tted with 'a baflle 38 to aid in separating the condensate into two layers of different gravity. The light layer ows through lines 43 and 23 to the main column I0 as reilux, but apart of it may be bypassed through line 4| and introduced into the lower part of the column in order to facilitatethe control of the dehydrating operation. The heavy layer is pumped through Ithrough line 18.

iainder `may be returned by the line 56 to the main column -I3. 'According to the operating conditions selected, some alcohol and even some water vapors may also go *overheadl through line 50.

The water and alcohol-mixture which leavesv column 40 through line 52 is charged to column 80,

which` may also be heated by a suitable reboiler $2.

In this column the alcohol is concentrated and is removed as the overhead through line 64;

the waterfis removed asy the bottoms through the line 66 and may be additionally cooled in cooler 61. The concentrated alcohol vapors are suitably condensedas by the condenser `68; some of' the condensatefrom receiver 83a is used as reflux for column and is returned .through line I9, and the remaining condensate is pumped through line 1li by pump 1l to join the initial concentrated alcohol feed in line 25.`

It may often be found desirable to supplement the subcooling and layer-forming ellect produced in coolers 34 and 43 by adding water to the condensate from condenser 32 and to the lower cost is thereby eifected inasmuch as such water v need not be entirely stripped of its valcohol content. Such water may be added in'controlled amount to the condensate from condenser 32 as through line 14 and to the lower layer from separator 36fas through line 15. lf desired or found necessary,

water from an external source may be introduced Cooling coil 11 may be positionedin line 13 to provide any necessary cooling of the low alcohol content water removed from' column B0. Pump 18 maybe provided to permit return of the dilute alcohol solution to the separators 36 and 44.

summarizing the operations in accordance with i exampl'e, approximately 34% of alcohol, `62% of gasoline, and 4% of water. The bottoms comprises a water-free blend oi alcohol and gasoline 42 as by pump 42a into a second subcooler 43 which is provided with articial refrigeration to induce a further separation into layers. The additionally subcooled condensate then ilows into a second separator 44 provided with balde 44a wherein another separation into two layers takes place. The lighter layer separated in the second separator 44 flows through line 40a.` and may be used as reflux in the main column l0.

The heavier layer from the secondary separator 44 passes through line 4'5 into column 43 which may be heated by reboiler 48 and whiz-h eifects a separation of the gasoline as the over head removed through line 5l! from the water and alcohol as the bottoms Iremoved through line 32. Gasoline vapors may be suitablyv condensed as in condenser 54;-part of the condensate may be-used to reiiux column 4i as at 53, and thereline. By subcooling the ternary azeotrope condensate, I am able to remove a lower layer which contains little gasoline and an upper layer which is rich in gasoline and which canbe returned as l In the condensing and subcooling of the overhead from distillation column I0, I find that it is most convenient and economical to subcool the condensate from condenser 32 in cooler 34 to about 65-75" F. inasmuch as this result can be accomplished with the average cooling water. In

Vthe articially refrigerated cooler 43, the temperature of the lower layer removed from separator 33 is most economically reduced to about' 30-40" F. `These'temperature 'reduction' stages For this purpose I have found that the give especially good results in the recovery of the gasoline and alcohol from the overhead from column I0. It will also be appreciated that the water may be added to the condensate either simul-- -at super-atmospheric pressures which may range as high as 100 lbsQ/sq. in. ormore. At the higher pressures better results can be obtained inasmuch asv less gasoline is removed inthe overhead vapors i from column i; and, hence more gasoline is directly incorporated into the ultimate motor fuel blend. When .operated at superatmospherlc pressure, it is preferable to have the column 4B at a pressure slightly higherthan the pressure in column Ill so that the overhead vapors may return as such to column I0 through line 56. Suitable means may be provided to separate out the necessary reux for column 46`as is wellknown, and the customary pressure and reliefl valves may also beprovided. Preferably column 60 is normally operated at atmospheric pressure.

Although I have described my 'improved distillation procedure in connection 'with the formation ofy an alcohol-gasoline blend, certain features thereof are applicable to the dehydration of concentrated alcohol for-the production of absolute alcohol. For example, column ivmay be used for the production oi absolute alcohol, which may be .removed through bottoms line I4; and columns 46 and B0 may be used for the recovery of the alcohol and the third material utilized to remove the water contained in the overhead vapors i'rom column i0. In such case, low alcohol content water maybe conveniently and economically withdrawn from thebase of column -80 as throughv line 13 and added to the condensate from condenser 32 and to the lower layer from separator 3 6 to aid in the desired layer formation. It will be appreciated that, in either operation, the third material such as gasoline is desirably substantially immiscible with water.

I have thus provided an improved process to remove continuously the water initially contained from a mixture of concentrated aqueous alcohol Y and gasoline, which comprises distilling said con@ per layer oi which comprises substantially anhy= drous alcohol and gasoline, using said upper.- layer as reflux for said distillation zone, removing. a

stable substantially anhydrous gasoline-alcohol motor fuel as a bottoms product from said distillation zone, preliminarily separating any gasoline contained in said lower layer in a second distillation zone in the overhead therefrom, fraction- V'ally separating said gasoline-free lower layer in 'a third distillation zone to recover concentrated alcohol as the overhead therefrom, recirculating tot said concentrated alcohol to said rst distillation zone, withdrawing substantially alcohol-free water as the bottoms from said third distillation zone, removing low alcohol content water from a point near the bottom of said third distillation zone, and adding said low alcohol content water to the overhead condensate from 'said flrst distillation zone to facilitateseparation of said condensate into the layers of liquids.

material, and water as overhead, condensing said azeotrope, subcooling the resulting condensate to obtain upper yand lower layers oi' liquids, the upper layer of which comprises substantially anhy drous alcohol and the third material, using said upper layer as reflux for said distillation zone, removing substantially anhydrous alcohol free of said third material as a. bottoms product from' said distillation zone, prelimlnarily separating any of the third material contained in said lower layer in a second distillation zone in the overhead therefrom, fractionally separating said third material-free lower layer in a third distillation zone to recover concentrated alcohol as the overhead therefrom, recirculating said concentrated alcohol to said first distillation zone, withdrawing substantially alcohol-free water as the bottoms from said third distillation zone, removing low alcohol content water from a pointnear the bottom of said third distillation zone, yand adding said low alcohol content water to the overhead condensate from said rst distillation zone to iacilitate separation of .said condensate into the layers of liquids.

3. The method as claimed in claim 1 which includes further subcooling the lower-condensate layer to form a second set of upper and lower layers, the upper of which comprises a further quantity of substantially anhydrous alcohol and A gasoline, utilizing the second upper layer as additional reflux for the nrst distillation zone, fractionally separating the second lower layer, after removal in the second distillation zone of any gasoline contained therein, in the third distillation zone to recover concentrated alcohol as the overhead, therefrom, and adding low alcohol content water to thelower condensate layer to facile itate `separation thereof into layers.

4. 'I'he method as claimed in claim 2 which includes further subcooling the lower condensate layer to form a second set of upper and lower layers, the upper 'of which comprises a further quantity of substantially anhydrous alcohol and the third material, utilizing the second upper layer as additional redux for the rst distillation zone, ractionally separating the 'second lower layer, after 'removal in the second distillation zone of any oi the third material contained therein, in thethird distillation zone to recover'concentrated alcohol asthe overhead therefrom, and adding low alcohol content water to'the lower condensate layer to facilitate separation thereof into layers.

- ALFRED S. WOLFNER. 

